JPH08143550A - Hydrazone compound and electrphotographic photoreceptor using the same compound and organic electroluminescent element - Google Patents

Abstract

PURPOSE: To obtain a new hydrazone compound excellent in photoreceptor characteristics of sensitivity, durability, etc., hole-transporting ability, thermal stability and thin film-forming property and useful as a photosensitive layer for electrophotographic photoreceptors, a hole transporting agent for organic electroluminescent elements. CONSTITUTION: This compound is expressed by formula I [Ar1 is a (substituted) phenylene, naphthylene, etc.; Ar2 is a (substituted) aryl; R1 and R2 are each H, a halogen, an alkyl, etc.; R3 is an alkyl, a (substituted) aryl; Z is ethylene or vinylene; (n) is 0 or 1], e.g. 4-[5-(10,11-dihydro-5H-dibenzo[b, f]azepinyl)]benzaldehyde-N,N-diphenylhydrazone. The compund of formula is obtained by reacting a compound of formula II with a compound of formula III in an inert organic solvent such as THF, as necessary, having a reaction promotor such as hydrocaloric acid at 10-120 deg.C, especially 25-80 deg.C.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel hydrazone compound useful as a charge transport agent used in electrophotographic photoreceptors and organic electroluminescent devices, and electrophotographic photoreceptors and organic electroluminescence using the compounds. Regarding the device.

[0002]

2. Description of the Related Art An electrophotographic method is generally a method in which the surface of a photoconductor made of a photoconductive material is charged in the dark, for example, by corona discharge, and then exposed to the light to selectively dissipate the charge in the exposed area. It is a kind of image forming method in which an electrostatic latent image is dispersed to obtain an electrostatic latent image, which is visualized with toner, and then transferred and fixed on paper or the like to obtain an image. As the photoconductor, an inorganic photoconductor containing an inorganic photoconductive compound such as selenium, zinc oxide, cadmium sulfide, or silicon as a main component, and a charge generating agent and a low-molecular weight or high-molecular weight charge transport agent in a binder resin There is an organic photoconductor using an organic compound dispersed in. Inorganic photoconductors have many advantages and have been widely used until now.For example, selenium is difficult to produce, its production cost is high, it is vulnerable to heat and mechanical shock, and it easily crystallizes, resulting in poor performance. Resulting in. Zinc oxide and cadmium sulfide have problems in moisture resistance and mechanical strength, and the dye added as a sensitizer is deteriorated by electrification and exposure, resulting in poor durability. Silicon is also difficult to manufacture and uses a highly irritating gas, so it is expensive and sensitive to humidity.

In recent years, organic photoreceptors using various organic compounds have been studied and widely used for the purpose of overcoming the drawbacks of these inorganic photoreceptors. Organic photoreceptors include a single-layer photoreceptor in which a charge generating agent and a charge transporting agent are dispersed in a binder resin, and a laminated photoreceptor in which a charge generating layer and a charge transporting layer are functionally separated. The function-separated type organic photoconductor has been extensively researched and widely used because of its wide choice of materials and the fact that a photoconductor having any desired performance can be produced relatively easily by combining them.

Examples of the charge generating agent include azo compounds,
Many organic compounds such as bisazo compounds, trisazo compounds, tetrakisazo compounds, thiapyrylium salts, squarylium salts, azurenium salts, cyanine dyes, perylene compounds, metal-free or metal phthalocyanine compounds, polycyclic quinone compounds, thioindigo compounds, or quinacridone compounds. Pigments and dyes have been proposed and put into practical use.

As the charge transfer agent, for example, Japanese Patent Publication No. 34-
Oxadiazole compounds described in JP-A-5466, JP-A-56
No. 123544, Oxazole Compound, Japanese Examined Patent Publication No. 5
JP-A 2-41880, Pyrazoline Compound, JP-B-55
-42380 gazette and Japanese Patent Publication No. 61-40104 gazette,
JP-B-62-35673, JP-B-63-3597
No. 6, hydrazone compound, Japanese Patent Publication No. 58-32372
Compounds disclosed in Japanese Patent Publication No. 63-18738, Japanese Patent Publication No. 63-19867, and Japanese Patent Publication No. 3-393.
No. 06 stilbene compound, JP-A-62-3025
For example, there is a butadiene compound disclosed in Japanese Patent No. Organic photoconductors using these charge-transporting materials have excellent properties and some have been put into practical use, but those that sufficiently satisfy the properties required for electrophotographic photoconductors have not yet been obtained. The current situation is not.

Further, electroluminescence devices having organic compounds as constituent elements have been studied in the past, but sufficient light emission characteristics have not been obtained. However, in recent years, the characteristics have been remarkably improved by adopting a structure in which several kinds of organic materials are laminated, and since then, studies on electroluminescent devices using organic materials have been actively conducted. This electroluminescent device having a laminated structure is manufactured by Kodak C.I. W. First reported by Tang et al. (Appl.Phys.Lett.51 (1987) 913), of which 1
Light emission of 1000 cd / m ² or more is obtained at a voltage of 0 V or less, and it has markedly higher characteristics than the inorganic electroluminescent elements that have been practically used in the past require a high voltage of 200 V or more. It has been shown.

These laminated electroluminescent devices have a structure in which an organic phosphor, an organic substance having a charge transporting ability, that is, a charge transporting agent and electrodes are laminated, and charges (holes and electrons) injected from the respective electrodes are laminated. ) Migrates through the charge transport agent, and they recombine to emit light. As the organic fluorescent substance, 8-quinolinol aluminum complex and organic dyes which emit fluorescence such as coumarin are used. Various compounds well known as organic materials for electrophotographic photoreceptors have been studied as charge transport agents, and for example, N, N'-di (3-tolyl) -N, N'-.
Diphenyl-4,4'-diaminodiphenyl or 1,1-
Examples thereof include diamine compounds such as bis [N, N, -di (4-tolyl) aminophenyl] cyclohexane and hydrazone compounds such as 4-diphenylaminobenzaldehyde-N, N-diphenylhydrazone. Furthermore, porphyrin compounds such as copper phthalocyanine have also been used.

By the way, although the organic electroluminescent device has high light emitting characteristics, it is not sufficient in terms of stability at the time of light emission and storage stability, and has not been put to practical use. As one of the problems in the stability of the device when emitting light and the storage stability,
The stability of the charge transport agent has been pointed out. The layer formed of the organic material of the electroluminescent device is very thin, 50 to several hundred nanometers, and the voltage applied per unit thickness is very high. In addition, light is also emitted or heat is generated by energization. Therefore, the charge transfer agent is required to have electrical, thermal or chemical stability. In addition, the charge transport layer in the device is generally in an amorphous state, but there is a phenomenon that luminescence occurs or crystallization occurs with time due to storage, which causes light emission to be hindered or device damage. Has been. For this reason, the charge transport agent is required to have a property of easily forming an amorphous state, that is, a glass state, and stably maintaining it.

Regarding the stability of the light emitting element due to such a charge transport material, for example, some diamine compounds and porphyrin compounds are electrically and thermally stable and have relatively high light emitting characteristics. However, deterioration of the element due to crystallization has not been solved. Further, a hydrazone compound having a simple structure is not preferable in terms of electrical and thermal stability.

[0010]

The charge transfer agent used in the organic photoreceptor has not only the sensitivity and other characteristics as a photoreceptor, but also a chemical stability that withstands light, ozone, and electrical loads. Stability and durability are required so that the sensitivity does not decrease even after repeated use or long-term use. In addition, as the charge transport material used in the organic electroluminescent device, an organic electroluminescent device satisfying various properties as an organic electroluminescent device such as light emitting properties and having excellent stability during light emission and storage stability can be used. Realizable film-forming properties and stability to withstand heat, oxygen, and electrical loads are required. The object of the present invention is to realize an electrophotographic photosensitive member which satisfies the characteristics of the photosensitive member and has high sensitivity and high durability, and an organic electroluminescent element which is excellent not only in the light emitting characteristics but also in stability during light emission and storage stability. The present invention provides a novel hydrazone compound useful as a charge transporting agent, an electrophotographic photoreceptor using the compound, and an organic electroluminescence device.

[0011]

According to the present invention, there is provided a hydrazone compound represented by the following general formula (1) and a photosensitive layer containing the compound on a conductive support for electrophotography. There is provided an organic electroluminescent device comprising a photoreceptor and the compound as a charge transport material.

[0012]

[Chemical 4]

(Wherein Ar ₁ represents a phenylene group, a naphthylene group, a biphenylene group, or an anthrylene group which may have a substituent, Ar ₂ represents a substituted or unsubstituted aryl group, and R ₁ and R ₂ independently represent a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group,
R ₃ represents an alkyl group, a substituted or unsubstituted aralkyl group or a substituted or unsubstituted aryl group, Z represents an ethylene group or a vinylene group, and n represents 0 or 1. ) In the present invention, the hydrazone compound represented by the general formula (1) used as the charge transporting agent is a novel compound, and is generally synthesized by a condensation reaction between a corresponding aldehyde compound and a hydrazine compound. For example, the following general formula (2)

[0014]

Embedded image

(Wherein Ar ₁ and R ₁ , R ₂ and Z have the same meanings as in the general formula (1)) and the following general formula (3)

[0016]

[Chemical 6]

(In the formula, Ar ₂ and R ₃ are represented by the general formula (1)
Means the same as. ) With a hydrazine derivative represented by the formula (1), toluene, alcohol, acetone, N, N-dimethylformamide, dimethylsulfoxide, tetrahydrofuran, dioxane and the like in an inert organic solvent, if necessary, p-toluenesulfonic acid, hydrochloric acid, 10 to 120 ° C., preferably 25 to 8 using an acid catalyst such as sulfuric acid or acetic acid or a reaction accelerator such as sodium acetate
It is obtained by reacting under a temperature condition of 0 ° C. Alternatively, an aldehyde compound represented by the above general formula (2) and the following general formula (4)

[0018]

[Chemical 7]

(Ar ₂ has the same meaning as in the above general formula (1)) and a hydrazine derivative represented by the general formula (1), toluene, alcohol, acetone, N, N-dimethylformamide,
If necessary, in a reaction reagent and an inert organic solvent such as dimethyl sulfoxide, tetrahydrofuran or dioxane, p
-Obtained by reacting with an acid catalyst such as toluenesulfonic acid, hydrochloric acid, sulfuric acid, or acetic acid or a reaction accelerator such as sodium acetate under temperature conditions of 10 to 120 ° C, preferably 25 to 80 ° C. The following general formula (5)

[0020]

Embedded image

(Wherein Ar ₁ , Ar ₂ , R ₁ , R ₂ and Z
Represents the same meaning as in the general formula (1). ), A hydrazone compound represented by the following general formula (6)

[0022]

[Chemical 9]

(In the formula, R ₃ has the same meaning as described above, and X 3
Represents a chlorine atom, a bromine atom, an iodine atom, a sulfonic acid residue, or the like. ) Is used as a reaction agent for toluene, xylene, dichlorobenzene, nitrobenzene, N, N-dimethylformamide, N-methylpyrrolidone, alcohol, dioxane, etc. 10 to 200 ° C., preferably 30 ° C. in the presence of a deoxidizing agent such as sodium hydroxide, potassium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate, triethylamine, pyridine, etc. in an inert organic solvent. It is obtained by reacting under a temperature condition of 120 ° C.

Specific examples of the compound according to the present invention which can be used as the charge transport agent include the following.

Compound No (1)

[Chemical 10]

Compound No (2)

[Chemical 11]

Compound No. (3)

[Chemical 12]

Compound No (4)

[Chemical 13]

Compound No. (5)

Embedded image

Compound No (6)

[Chemical 15]

Compound No. (7)

Embedded image

Compound No. (8)

[Chemical 17]

Compound No. (9)

Embedded image

Compound No. (10)

[Chemical 19]

Compound No. (11)

Embedded image

Compound No. (12)

[Chemical 21]

Compound No (13)

[Chemical formula 22]

Compound No (14)

[Chemical formula 23]

Compound No. (15)

[Chemical formula 24]

Compound No (16)

[Chemical 25]

Compound No. (17)

[Chemical formula 26]

Compound No. (18)

[Chemical 27]

Compound No. (19)

[Chemical 28]

Compound No (20)

[Chemical 29]

Compound No (21)

Embedded image

Compound No (22)

[Chemical 31]

Compound No (23)

Embedded image

Compound No (24)

[Chemical 33]

Compound No. (25)

Embedded image

Compound No. (26)

Embedded image

Compound No (27)

Embedded image

Compound No (28)

Embedded image

Compound No (29)

[Chemical 38]

Compound No (30)

[Chemical Formula 39]

Compound No (31)

[Chemical 40]

Compound No (32)

Embedded image

The electrophotographic photoreceptor of the present invention has a photosensitive layer containing one or more of the above hydrazone compounds. There are various forms of the photosensitive layer, and any of them may be used as the photosensitive layer of the electrophotographic photosensitive member of the present invention. As a typical example, the photoreceptor is shown in FIGS.

The photoconductor of FIG. 1 comprises a conductive support 1 and a photosensitive layer 2 comprising a hydrazone compound, a sensitizing dye and a binder resin. The photoconductor of FIG. 2 is such that a photoconductive layer 21 in which a charge generating substance 4 is dispersed in a charge transport medium 3 composed of a hydrazone compound and a binder resin is provided on a conductive support 1. In this photoreceptor, the charge generating substance absorbs light to generate charge carriers, which are then transported by the charge transport medium. In this case, the charge transport material is preferably transparent to the light that generates the charge carriers. The hydrazone compound satisfies the condition that the absorption wavelength range does not overlap with the charge generating substance, with only a slight absorption in the low wavelength range from the ultraviolet to the visible region.

The photoconductor of FIG. 3 comprises a photoconductive layer 22 formed by laminating a charge generation layer 5 mainly composed of a charge generation substance 4 and a charge transport layer 3 composed of a hydrazone compound and a binder resin on a conductive support 1. It is provided. In this photoreceptor, the charge transport layer 3
The light that has passed through reaches the charge generation layer 5 and the charge generation substance 4
Are absorbed by the carrier and charge carriers are generated. The charge carriers are injected and transported in the charge transport layer 3. The photoreceptor of FIG.
The photosensitive layer 23 in which the charge generating layer 5 and the charge transporting layer 3 of the photoconductor of FIG. Generation and transport of charge carriers can be explained by the same mechanism as described above. The photosensitive member of FIG. 5 has a photosensitive layer 24 in which a protective layer 6 is further laminated on the charge generation layer 5 of the photosensitive member of FIG. 4 for the purpose of improving mechanical strength.

The photoconductor of the present invention as exemplified above is manufactured by a conventional method. For example, the above general formula (1)
It is prepared by dissolving the hydrazone compound represented by in a suitable solvent together with a binder resin, and adding a charge generating substance, a sensitizing dye, an electron-withdrawing compound or a plasticizer, a pigment, and other additives as necessary. It can be produced by applying a coating liquid of the above onto a conductive support and drying it to form a photosensitive layer of several μ to several tens μ. In the case of a photosensitive layer composed of two layers of a charge generation layer and a charge transport layer, the above-mentioned coating solution is applied onto the charge generation layer, or the charge generation layer is applied onto the charge transport layer obtained by applying the above-mentioned coating solution. It can be manufactured by forming. Further, the photoreceptor thus manufactured may be provided with an adhesive layer, an intermediate layer, and a barrier layer, if necessary.

Solvents for preparing the coating solution include tetrahydrofuran, 1,4-dioxane, methyl ethyl ketone,
Examples thereof include polar organic solvents such as cyclohexanone, acetonitrile, N, N-dimethylformamide and ethyl acetate, aromatic organic solvents such as toluene and xylene, and chlorinated hydrocarbon solvents such as dichloromethane and dichloroethane. A solvent having a high solubility for the hydrazone compound and the binder resin is preferably used.

Examples of the sensitizing dyes include triarylmethane dyes such as methyl violet, brilliant green, crystal violet and acid violet, xanthene dyes such as rhodamine B, eosin S and rose bengal, and thiazine dyes such as methylene blue. Examples thereof include pyrylium dyes such as benzopyrylium salts, thiapyrylium dyes, and cyanine dyes.

Examples of the electron-withdrawing compound which forms a charge transfer complex with a hydrazone compound include chloranil, 2,3-dichloro-1,4-naphthoquinone, 1-nitroanthraquinone, 2-chloroanthraquinone and phenanthrenequinone. Quinones, aldehydes such as 4-nitrobenzaldehyde, 9-benzoylanthracene, indandione, 3,5-dinitrobenzophenone, 2,4,7-trinitrofluorenone, 2,4,4.
Ketones such as 5,7-tetranitrofluorenone, acid anhydrides such as phthalic anhydride and 4-chloronaphthalic anhydride,
Tetracyanoethylene, terephthalalmalenonitrile,
Cyano compounds such as 9-anthrylmethylidenemalenonitrile, 3-benzalphthalide, 3- (α-cyano-p-
Nitrobenzal) -4,5,6,7-tetrachlorophthalide and other phthalides.

As the binder resin, polymers and copolymers of vinyl compounds such as styrene, vinyl acetate, vinyl chloride, acrylic acid ester, methacrylic acid ester, butadiene, polyvinyl acetal, polycarbonate, polyester, polyphenylene oxide, polyurethane, Various resins that are compatible with the hydrazone compound, such as cellulose ester, phenoxy resin, silicon resin, and epoxy resin, can be mentioned. The amount of the binder resin used is usually 0.4 to 10 times by weight, preferably 0.5 to 5 times by weight, the amount of the hydrazone compound.

The photosensitive layer of the present invention may contain a well-known plasticizer for the purpose of improving film-forming property, flexibility and mechanical strength. Examples of the plasticizer include phthalic acid ester, phosphoric acid ester, chlorinated paraffin, methylnaphthalene, epoxy compound, chlorinated fatty acid ester and the like.

Further, as the conductive support on which the photosensitive layer is formed, the materials used in the well-known electrophotographic photosensitive members can be used. For example, a metal drum such as aluminum, stainless steel or copper, a sheet or a laminate of these metals, a vapor deposition product, a metal powder, carbon black, copper iodide or a conductive substance such as a polymer electrolyte is applied together with an appropriate binder. Conductive treated plastic film,
Examples thereof include a plastic drum, paper, a paper tube, and a plastic film and a plastic drum which are made conductive by containing a conductive substance.

Further, according to the present invention, it is possible to obtain an organic electroluminescence device using the hydrazone compound represented by the general formula (1) as a hole transport layer. There are two-layer structure and three-layer structure of organic electroluminescent devices. These layer structures are provided on a transparent electrode which is a substrate, and a counter electrode is provided thereon to form an organic electroluminescent device. In the case of a two-layer structure,
A combination of a hole transport layer and an electron transport light emitting layer or a combination of an electron transport layer and a hole transport light emitting layer. In the case of a three-layer structure, a structure in which a light emitting layer is sandwiched between a hole transport layer and an electron transport layer is used. Become. The structure according to the present invention has a two-layer structure of a hole-transporting layer and an electron-transporting light-emitting layer or a three-layer structure in which an electron-transporting layer is further laminated thereon. FIG. 6 shows an organic electroluminescent device having a two-layer structure. In the organic electroluminescent device of FIG. 6, a transparent electrode 8 is provided on a support 7, and a hole transport layer 9, an electron transport light emitting layer 10 and an electrode 11 are further provided thereon.

Examples of the electron-transporting luminescent agent include tris (8-quinolinol) aluminum, bis (8-quinolinol) magnesium, and tris (5-chloro-8-).
Quinolinol) chelated oxinoid compounds such as gallium, coumarin derivatives, perylene pigments and chelated 2,
Examples thereof include a chelate compound of a 2′-bipyridine compound and a salicylidene-O-aminophenol derivative.

Examples of the electron transfer agent include 2-
(4-tert-Butylphenyl) -5- (4-biphenylyl) -1,3,5-oxadiazole, 2,4,7
-Trinitro-9-fluorenone, 4-butoxycarbonyl-9-dicyanomethylidenefluorene, 3,3'-
Bis (tert-butyl) -5,5'-dimethyl-4,
4'-diphenoquinone, 3,5'-bis (tert-butyl) -5,3'-dimethyl-4,4'-diphenoquinone, 3,5, -bis (tert-butyl) -3 ', 5'
-Dimethyl-4,4'-diphenoquinone and the like.

Glass, plastic, quartz, etc. are used for the support of the organic electroluminescence device, and metal such as gold, aluminum, indium, silver, magnesium or indium tin oxide (IT) is used on this substrate.
O), tin oxide, zinc oxide, and other thin film electrodes are formed by vapor deposition to form semitransparent or transparent electrodes. A charge transport layer or a light emitting layer is laminated on this, and an electrode similar to that described above is further formed thereon to form an organic electroluminescence device, and a DC voltage is applied to this to emit light.

[0071]

The present invention will be described below in detail with reference to examples. Parts in the examples represent parts by weight.

Example 1 (Synthesis Example of Compound No. 2) 4- [5- (10,11-dihydro-5H-dibenzo [b, f] azepinyl)] benzaldehyde 29.9 parts and N, N-diphenyl Hydrazine hydrochloride 24.3
Parts in 500 parts of tetrahydrofuran and 2 at 50 ° C.
Stir for hours. After the reaction was completed, it was poured into 2000 parts of water, and the precipitated crystals were collected by filtration. The obtained crystals were washed with ethyl alcohol and dried under reduced pressure. Column chromatography (carrier; silica gel, eluent; toluene / hexane = 1)
/ 2) to give 4- [5- (10,11-dihydro-5H-dibenzo [b, f] azepinyl)] benzaldehyde-N, N-diphenylhydrazone 27.3 parts (yield 58.6%). ) Got. Melting point is 196.0-19
It was 7.0 ° C. The elemental analysis values are shown in Table 1 below as C ₃₃ H ₂₇ N ₃ .

[0073]

[Table 1]

The infrared absorption spectrum (KBr tablet method) is shown in FIG.

Example 2 (Synthesis Example of Compound No. 21) 4- [5- (5H-dibenzo [b, f] azepinyl)]
29.7 parts of benzaldehyde and 13.4 parts of N, N-methylphenylhydrazine were added to tetrahydrofuran 500.
1 part of glacial acetic acid, and the mixture was stirred at 50 ° C. for 3 hours. After the reaction was completed, it was poured into 2000 parts of water, and the precipitated crystals were collected by filtration. The obtained crystals were washed with ethyl alcohol and dried under reduced pressure. Recrystallize with ethyl acetate to 4- [5
-(5H-dibenzo [b, f] azepinyl)] benzaldehyde-N, N-methylphenylhydrazone 28.9
Parts (yield 72.0%) were obtained. Melting point is 195.0-19
It was 7.0 ° C. The elemental analysis values are shown in Table 2 below as C ₂₈ H ₂₃ N ₃ .

[0076]

[Table 2]

The infrared absorption spectrum (KBr tablet method) is shown in FIG.

Example 3 (Synthesis example of compound No. 1) 21.0 parts of 4- [5- (10,11-dihydro-5H-dibenzo [b, f] azepinyl)] benzaldehyde and N, N-methyl 12.0 parts of phenylhydrazine was dissolved in 500 parts of tetrahydrofuran, 1 part of glacial acetic acid was added, and the mixture was stirred at room temperature for 3 hours. After the reaction was completed, the reaction product was poured into 2000 parts of water, and the precipitated crystals were collected by filtration. The obtained crystals were washed with ethyl alcohol and dried under reduced pressure. This was purified by column chromatography (carrier; silica gel, eluent; toluene / hexane = 2/3) to give 4
-[5- (10,11-Dihydro-5H-dibenzo [b, f] azepinyl)] benzaldehyde-N, N-
Methylphenylhydrazone 15.8 parts (yield 55.8
%) Was obtained. The melting point was 192.0-194.0 ° C. The elemental analysis values are shown in Table 3 below as C ₂₈ H ₂₅ N ₃ .

[0079]

[Table 3]

The infrared absorption spectrum (KBr tablet method) is shown in FIG.

Example 4 (Synthesis example of compound No. 22) 4- [5- (5H-dibenzo [b, f] azepinyl)]
23.8 parts of benzaldehyde and 26.5 parts of N, N-diphenylhydrazine hydrochloride were added to 50 parts of tetrahydrofuran.
It was dissolved in 0 part and stirred at room temperature for 3 hours. After the reaction was completed, the reaction product was poured into 2000 parts of water, and the precipitated crystals were collected by filtration. The obtained crystals were washed with ethyl alcohol and dried under reduced pressure. Next, it was dissolved in 100 parts of ethyl acetate, poured into 1000 parts of methyl alcohol, and crystallized to give 4- [5-
(5H-dibenzo [b, f] azepinyl)] benzaldehyde-N, N-diphenylhydrazone (28.9 parts, yield 77.9%) was obtained. Melting point is 178.0-179.0
° C. The elemental analysis values are shown in Table 4 below as C ₃₃ H ₂₅ N _3.
It was the street.

[0082]

[Table 4]

The infrared absorption spectrum (KBr tablet method) is shown in FIG.

Example 5 The following chlorodian blue was used as a charge generating agent.

[0085]

Embedded image

1.5 parts of polyester resin (Byron 2
00, manufactured by Toyobo Co., Ltd.) (18.5 parts of 8% THF solution), placed in an agate pot containing agate balls, and spun for 1 hour with a planetary fine pulverizer (Frits) to disperse. The obtained dispersion liquid was applied onto the aluminum surface of an aluminum vapor-deposited PET film having a conductive support by using a wire bar, and dried under normal pressure at 60 ° C. for 2 hours and further under reduced pressure for 2 hours to give a film thickness of 0.3 μm. The charge generation layer of was formed. On the other hand, Compound No. 1.5 parts of the hydrazone compound of 1 was added to 18.75 parts of a 8% dichloroethane solution of a polycarbonate resin (Panlite K-1300, manufactured by Teijin Chemicals Ltd.), and ultrasonic waves were applied to completely dissolve the hydrazone compound. This solution was coated on the charge generation layer with a wire bar and dried under normal pressure at 60 ° C. for 2 hours and further under reduced pressure for 2 hours to form a charge transport layer having a film thickness of about 20 μm. 1 was produced. The sensitivity of this photoconductor was measured using an electrostatic copying paper test device (trade name "EPA-8100" manufactured by Kawaguchi Electric Co., Ltd.). First, the photoreceptor is charged by a corona discharge of −8 kV in the dark, and then exposed to 3.0 lux of white light, and the time (seconds) until the surface potential is reduced to half of the initial surface potential is measured. The half-exposure amount E1 / 2 (lux seconds) was determined. The initial surface potential of this photosensitive member was -1090 V, and E1 / 2 was 1.7 lux seconds.

Examples 6 to 18 Example 5 except that the charge generating agent and the charge transporting agent (hydrazone compound) in Example 5 were replaced with those shown in Tables 5 to 6.
Photoconductor No. 2-14 were produced. Photoconductor No. The results of 2 to 14 are shown in Tables 7 to 8.

[0088]

[Table 5]

[0089]

[Table 6]

[0090]

[Table 7]

[0091]

[Table 8]

Example 19 As a charge generating agent, 1.5 parts of α-TiOPc was added to 50 parts of a 3% THF solution of polyvinyl butyral resin (S-REC BX-L, manufactured by Sekisui Chemical Co., Ltd.) and the mixture was mixed with an ultrasonic disperser at 45 parts. Dispersed for minutes. The obtained dispersion liquid was applied onto the aluminum surface of the aluminum vapor-deposited PET film of the conductive support using a wire bar, dried under normal pressure at 60 ° C. for 2 hours, and further dried under reduced pressure for 2 hours to give a film thickness of 0.3 μm. The charge generation layer of was formed. On the other hand, Compound No. 1.5 parts of the hydrazone compound of 1 was added to 18.75 parts of a 8% dichloroethane solution of a polycarbonate resin (Panlite K-1300, manufactured by Teijin Chemicals Ltd.), and ultrasonic waves were applied to completely dissolve the hydrazone compound. This solution was coated on the charge generation layer with a wire bar and dried under normal pressure at 60 ° C. for 2 hours and further under reduced pressure for 2 hours to form a charge transport layer having a thickness of about 20 μm. 15 was produced. About this photoconductor, an electrostatic copying paper testing device (trade name "EPA-8
100 ") was used to measure the sensitivity. First, the photoconductor is charged in a dark place by corona discharge of -8 kV, and then exposed to monochromatic light of 800 nm with a light amount of 0.4 μW / cm ² , and the amount of energy until the surface potential is reduced to half of the initial surface potential. Then, the half-exposure dose E1 / 2 (μJ / cm ² ) was measured. The initial surface potential of this photoconductor is -1085V,
E1 / 2 was 0.51 μJ / cm ² .

Example 20 As a charge generating agent, the following trisazo compound was used instead of α-TiOPc.

[0094]

Embedded image

The same procedure as in Example 19 was carried out except that No. 16 was produced. Example 19
When the sensitivity was measured in the same manner as above, the initial surface potential was -1125 V and E1 / 2 was 0.48 μJ / cm ² .

Example 21 The following thiapyrylium salt as a charge generating agent

[0097]

[Chemical 47]

0.1 part, Compound No.
10 parts of 18 hydrazone compounds are 8% of polycarbonate resin (Panlite K-1300, Teijin Chemicals Ltd.)
To the dichloroethane solution (125 parts), ultrasonic waves were applied to completely dissolve the thiapyrylium salt and the hydrazone compound. This solution is applied on the aluminum surface of an aluminum vapor-deposited PET film which is a conductive support using a wire bar, and dried under normal pressure at 60 ° C. for 2 hours and further under reduced pressure for 2 hours to form a photosensitive layer having a film thickness of 15 μm. Form the photoconductor No. 17 was produced. The sensitivity of this photoconductor was measured using an electrostatic copying paper tester (trade name "EPA-8100"). First, the photoreceptor is charged by +8 kV corona discharge in the dark, then exposed to 3.0 lux white light, and the time (sec) until the surface potential decreases to half of the initial surface potential is measured. The exposure amount E1 / 2 (lux seconds) was determined. The initial surface potential of this photoreceptor was +890 V, and E1 / 2 was 2.8 lux seconds.

Example 22 The coating solution of the charge transfer agent used in Example 5 was applied to aluminum vapor-deposited PE.
It was applied on the aluminum surface of the T film using a wire bar and dried under normal pressure at 60 ° C. for 2 hours and further under reduced pressure for 2 hours to form a charge transport layer having a film thickness of 10 μm. On the other hand, 3.0 parts of the same disazo compound used in Example 17 as a charge generating agent was added to 18.5 parts of an 8% THF solution of a polyester resin (Vylon 200, manufactured by Toyobo Co., Ltd.), and an agate pot containing agate balls was added. The mixture was placed in a flask and rotated with a planetary fine pulverizer (Frits Co., Ltd.) for 1 hour to disperse. To this dispersion, 200 ml of THF was added and mixed with stirring to obtain a coating liquid.
This coating solution is applied onto the charge transport layer by spraying,
It was dried under normal pressure at 60 ° C. for 2 hours and further under reduced pressure for 2 hours to form a charge generation layer having a thickness of 0.5 μm. Further, a solution in which an alcohol-soluble polyamide resin is dissolved in isopropanol is applied onto the charge generation layer by spraying, and an overcoat layer having a film thickness of 0.5 μm is formed under normal pressure at 60 ° C. for 2 hours and further under reduced pressure for 2 hours. At least the photoconductor No. 18 was produced. The sensitivity of this photosensitive member was measured in the same manner as in Example 5. The initial surface potential of this photoconductor is + 1030V, and E1
/ 2 was 2.2 lux seconds.

Comparative Example 1 Compound No. used in Example 5 The following hydrazone compounds instead of 1

[0101]

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A comparative photoconductor was prepared in the same manner as in Example 5 except that the above was used. The sensitivity of this photosensitive member was measured in the same manner as in Example 5. The initial surface potential of this photoconductor is -97.
At 0V, E1 / 2 was 4.5 lux seconds. A compound in which the hydrazine component has a ring-closed structure (a ring is formed by Ar ₂ and R ₃ ) has low drift mobility, resulting in decreased sensitivity.

Example 23 An ITO glass electrode (made by Matsuzaki Vacuum Co., Ltd., standard type of transparent conductive film) was used as a vapor deposition device (made by Vacuum Instrument Co., Ltd., LC-6).
Compound No. is added to the (F type) substrate holder. 2 {4- [5-
(10-11-dihydro-5H-dibenzo [b, f] azepinyl)] benzaldehyde-N, N-diphenylhydrazone} was added and the pressure was reduced to 1 × 10 ⁻⁶ Torr.
The heating boat was heated to perform vapor deposition at a vapor deposition rate of 12 nm / min. 2 hole transport layer was formed on the ITO glass electrode. Next, tris (8-quinolinol) aluminum was put in a heating boat, heated and vapor-deposited at a vapor deposition rate of 20 nm / min to form a light-emitting layer having a film thickness of 50 nm on the hole-transporting layer. Furthermore, 4 on it
An organic electroluminescent device was prepared by forming a magnesium vapor deposition film having a film thickness of 150 nm at a vapor deposition rate of 0 nm / min to form a counter electrode. When a DC voltage of 12 Volt was applied with the ITO electrode as the positive electrode and the magnesium electrode as the negative electrode, bright green light was emitted, and a luminance meter (LS-110 manufactured by Minolta Camera Co., Ltd.) was used.
Type) to measure the brightness of 1600 cd / m
² was shown. When a continuous lighting test was conducted at a luminance of 500 cd / m ^2, the luminance half-life was 200 Hr.

Example 24 Compound No. Instead of using compound 2, compound no. An organic electroluminescence device was prepared in the same manner as in Example 23 except that 17 {4- [5- (5H-dibenzo [b, f] azepinyl)] benzaldehyde-N, N-methylphenylhydrazone} was used. When a direct current of 13 Volt was applied, a bright green light was emitted with a brightness of 1400 cd / m ² . Further, when a continuous lighting test was conducted at a luminance of 500 cd / m ^2, the luminance half-life was 220 Hr.

[0105]

INDUSTRIAL APPLICABILITY The novel hydrazone compound of the present invention has an excellent hole transporting ability and can be widely used as a hole transporting material. Further, the electrophotographic photoreceptor of the present invention having a photosensitive layer containing these compounds on a conductive support exhibits excellent photoreceptor characteristics, and has the advantage that it can be widely used as an electrophotographic photoreceptor. The organic electroluminescent device of the present invention produced by using as a hole-transporting material these compounds, which has a thermal stability and forms a good thin film, exhibits excellent emission characteristics and is widely used as a display device. It has the advantage that it can be used.

[Brief description of drawings]

FIG. 1 is a sectional view of a single-layer photoconductor for electrophotography.

FIG. 2 is a cross-sectional view of a single-layer electrophotographic photoreceptor for electrophotography in which a charge generating substance is dispersed.

FIG. 3 is a cross-sectional view of an electrophotographic photoreceptor in which a charge generation layer and a charge transport layer are laminated in this order on a conductive support.

FIG. 4 is a cross-sectional view of an electrophotographic photoreceptor in which a charge transport layer and a charge generation layer are laminated in this order on a conductive support.

FIG. 5 is a sectional view of an electrophotographic photosensitive member provided with a protective layer.

FIG. 6 is a cross-sectional view of an organic electroluminescent device.

FIG. 7 shows an infrared absorption spectrum of compound No2.

FIG. 8 shows an infrared absorption spectrum of compound No21.

FIG. 9 shows an infrared absorption spectrum of compound No1.

FIG. 10 shows an infrared absorption spectrum of compound No22.

[Explanation of symbols]

 1 Conductive Support 2, 21, 22, 23, 24 Photosensitive Layer 3 Charge Transport Medium, Charge Transport Layer 4 Charge Generating Material 5 Charge Generating Layer 6 Protective Layer 7 Glass Substrate 8 ITO Electrode 9 Hole Transport Layer 10 Light Emitting Layer 11 Magnesium electrode

[Chemical 43]

[Chemical 44]

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 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Mitsutoshi Anzai 45 Miyukigaoka, Tsukuba-shi, Ibaraki Hodogaya Chemical Industry Co., Ltd. Tsukuba Research Institute

Claims (3)

[Claims] 1. The following general formula (1): (In the formula, Ar ₁ is a phenylene group which may have a substituent,
A naphthylene group, a biphenylene group, or an anthrylene group; Ar ₂ represents a substituted or unsubstituted aryl group; R ₁ and R ₂ are each independently a hydrogen atom, a halogen atom,
R ₃ represents an alkyl group or an alkoxy group, R ₃ represents an alkyl group, a substituted or unsubstituted aralkyl group or a substituted or unsubstituted aryl group, Z represents an ethylene group or a vinylene group, and n represents 0 or 1. ) A hydrazone compound represented by. 2. The following general formula (1): embedded image on a conductive support. (In the formula, Ar ₁ is a phenylene group which may have a substituent,
A naphthylene group, a biphenylene group, or an anthrylene group; Ar ₂ represents a substituted or unsubstituted aryl group; R ₁ and R ₂ are each independently a hydrogen atom, a halogen atom,
R ₃ represents an alkyl group or an alkoxy group, R ₃ represents an alkyl group, a substituted or unsubstituted aralkyl group or a substituted or unsubstituted aryl group, Z represents an ethylene group or a vinylene group, and n represents 0 or 1. ) A photoconductor for electrophotography, comprising a photosensitive layer containing a hydrazone compound represented by the formula (1). 3. An organic electroluminescent device comprising at least an electrode, a hole-transporting layer, a light-emitting layer and an electrode, which is used as a charge-transporting agent for the hole-transporting layer, represented by the following general formula (1): (In the formula, Ar ₁ is a phenylene group which may have a substituent,
A naphthylene group, a biphenylene group, or an anthrylene group; Ar ₂ represents a substituted or unsubstituted aryl group; R ₁ and R ₂ are each independently a hydrogen atom, a halogen atom,
R ₃ represents an alkyl group or an alkoxy group, R ₃ represents an alkyl group, a substituted or unsubstituted aralkyl group or a substituted or unsubstituted aryl group, Z represents an ethylene group or a vinylene group, and n represents 0 or 1. ) An organic electroluminescent device comprising at least one hydrazone compound represented by the formula (1).